Polyamides from xylylene diamines and phenylindan dicarboxylic acids



United States Patent 3,376,270 POLYAMIDES FROM XYLYLENE DIAMINES AND PHENYLINDAN DHCARBOXYLIC ACIDS James S. Ridgway, Durham, N.C., assignor to Monsanto Company, St. Louis, Mo., a corporation of Delaware N0 Drawing. Continuation-impart of application Ser. No.

457,828, May 21, 1965. This application Dec. 16, 1966,

Ser. No. 602,121

5 Claims. (Cl. 260-78) ABSTRACT OF THE DISCLOSURE Copolyamides are produced from hexamethylene diamine, adipic acid, xylylene diamine and a phenylindan dicarboxylic acid. These polyamides are useful in the fabrication of textile fibers which are characterized by having good sonic modulus retention.

CROSS-REFERENCES TO RELATED APPLICATIONS This application is a continuation-in-part of Ser. No. 457,828, filed May 21, 1965.

BACKGOUND OF THE INVENTION (1) Field of the invention This invention relates to copolyamides produced from dicarboxylic acids and diamines.

(2) Description of the prior art Polyamides, such as polyhexamethylene adipamide (nylon 66) and polycaproarnide (nylon 6) are well known in the art and have found significant commercial success both as textile fibers and as reinforcing fibers, such as tire cord. Although the textile fibers obtained from the previously known fiber-forming polyamides heretofore known are of great value, much research effort is being continuously expended in order to improve their properties. For example, previously known polyamides are opaque in appearance. In some commercial uses, for example, packaging material and fishing lines, it is desirable that the polyamide textile fibers be transparent. Furthermore, while, as pointed out above, previously known polyamides have found significant use in the reinforcement of rubber articles such as vehicle tires, an inherent drawback in their use to reinforce vehicle tires is their tendency to fiatspot. Flatspotting is a term used to describe the out-of-roundness than occurs when a polyamide reinforced vehicle tire is allowed to rest for a period of time. That portion of the tire which is in contact with the pavement becomes flattened and, when the vehcle is started again this flat spot causes vibration of the vehicle. While this phenomena of fiatspotting is not completely understood, it is thought that it is related to heat and moisture stability. There is, therefore, at present a great deal of efiiort being put into finding polyamides which have increased heat and moisture stability.

SUMMARY OF THE INVENTION The copolyamides of the present invention are useful in the production of shaped articles by extrusion, molding or casting in the nature of yarns, fabrics, films, pellicles, bearings, ornaments or the like. They are particularly useful in the production of textile fibers and as reinforcing cords produced therefrom.

3,376,270 Patented Apr. 2, 1968 The present invention provides a novel linear fiberforming copolyamide composed of (A) to 98 mole percent, based on the molecular weight of the copolyamide, of units represented by the structure r-r H 0 0 aaawcHtat j tawherein R is a member of the group consisting of hydrogen and alkyl groups containing 1 to 3 carbon atoms.

In a typical preparation the copolyamide is formed by interpolymerizing the desired proportions of adipic acid, hexamethylene diamine, xylylene diamine and a phenylinclan dicarboxylic acid. The acids and diamines may be added to the polymerization step as such or, as is preferred, they may be added in the form of salts prepared from one of the acids and one of the diamines. In any event, the amount of each component added to the polym erizer is determined by the amount desired in the copolymer product. Generally, the amounts of xylylene diamine and phenylindan dicarboxylic acid added to the polymerization step is sufiicient to provide from 2 to 30 mole percent in the copolymer of units having the structure wherein R is defined above. It has been found that at least about 2 mole percent is needed in order that the advantageous effects be realized. Amounts greater than 30 mole percent are usually to be avoided since the tenacity and melting point of the copolymer are adversely affected. The preferred amount of these units is between 5 and 20 mole percent.

The copolyamides of this invention are prepared by procedures Well known in the art and commonly employed in the manufacture of simple polyamides. That is, the reactants are heated at a temperature of from C. to 300 C. and preferably from 200 C. to 295 C. until the product has a sufiiciently high molecular weight to exhibit fiber-forming properties, which properties are reached when the copolyamide has an intrinsic viscosity of at least 0.4 The reaction can be conducted at superatmospheric, atmospheric, or subatmospheric pressure. Often it is desirable, especially in the last stage of the reaction, to employ conditions, e.g. reduced pressure, which will aid in the removal of the reaction byproducts. Preferably, the reaction is carried out in the absence of oxygen, for example, in an atmosphere of nitrogen.

Intrinsic viscosity as employed herein is defined as Lim C melt spun directly from the bottom of the autoclave to yield a mono-filament yarn having good textile properties. The increased stability to heat and moisture was demonstrated by the percent retention of sonic modulus 5 at rising temperatures, as shown in Table I and Table II;

TABLE I RH) Mole percent Mole percent Sonic Modulus 66 PX at 30 0 Percent Retained at- Example D-PDA 50 C. so 0. 110 0. 120 0. 150 0.

100 0 59. as 94 so as 55 33 9s 44. 0s s7 s5 74 63 48 so 10 45. 20 90 s3 76 64 40 s5 45. 90 7o c7 52 so 20 40. 79 94 92 so 66 m the preparation of the copolymers of the present m- 15 TABLE H (30% RH) vention may be represented by the formula:

Sonic Modulus Percent Retained at R Example at 30 C. o 0 C. C. 0. C. P; g' QH 75.22 83 70 57 4s 47. 4s 9s s3 69 c1 50.31 s 6:;

47.48 1 s 7 e 2 2 '1 B R 40. 19 9 9 80 I wherein R is as defined above. Typical suitable compounds falling within this formula are: 3-(4-carboxyphenyl)-5-indan carboxylic acid; 3-(3-carboxyphenyl)-5- indan carboxylic acid; 3-(4-carboxyphenyl)-l,1,3-trimethyl-S-indan carboxylic acid; 3-(3-carboxyphenyl)- 1,1,3-triethyl6-indan canboxylic acid; 3(4-carboxyphenyl)-1-methyl-1,3-dipropyl-5-indan carboxylic acid; 3- (4-carboxyphenyl)-l-rnethyl-1,3-diethyl-6-indan carboxylic acid, and-the like. The preferred phenylindan dicarboxylic acid for the preparation this inevntion is 3-(4 carboxyphenyl)-l,1,3-trimethyl-5- indan carboxylic acid which is represented by the formula:

The Xylylene diamine employed in producing the of the copolyamides of 1 The results shown in Table I and II conclusively indicate that the copolyamides of present invention are far superior, in regard to their heat and moisture stability,

than the conventional nylon 66. Furthermore, while the TABLE III (0% RH) copolymers of the present invention may be either the metaor the para-isomer.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In Examples 1-5 copolymers were prepared having the Mole percent Mole percent Sonic Modulus Percent Retained at- Example 66 PXD-IDA at 30 C.

50 C. 80 C. C. C. C.

95 5 44.1 92 S9 74 67 57 90 10 43. 0 93 89 S0 70 57 S5 15 38. 3 96 84 85 76 65 TABLE IV (30% RH) 50 Sonic Modulus Percent Retained at- Exarnple at 30 C.

45 C. 60 C. 75 C. 90 C.

6 47. 5 SS 76 67 58 7 43. O 91 80 70 (i5 8 40. 8 S8 S0 75 67 indicated molepercent of components. (66 represents hexamethylene adipamide units and MXD-PDA represents units from meta-xylylene diamine and 3-(4-carboxyphenyl)-1,1,3-trimethyl-5-indan carboxylic acid.) In each example the amount of each component employed was determined by its desired mole percentage in the copolymer. Salts of (1) hexamethylene diamine and adipic acid, (2) hexamethylene diamiue and 3-(4-carboxyphenyl)-1,1,3-trimethyl-5-indan carboxylic acid and (3) meta-xylylene diamiue and adipic acid were dissolved in water and the resulting solution was placed in a stainless steel, high pressure autoclave which had been previously purged with nitrogen. The temperature and pressure within the autoclave were slowsly raised until values of 220 C. and 250 p.s.i.g., respectively, were reached. The temperature was then further increased to 243 C. while the pressure was maintained at 250 p.s.i.g. by removal of steam condensate. The pressure was then gradually reduced to atmospheric over a 25-minute period. The temperature was allowed to level at 280 C.and the polymer allowed to equilibrate for 30 minutes. The polymer was H 7 l \T=(CH2)s-l 1'( i(CH2)4 C and 75 (B) 30 to 2 mole percent based on the molecular weight of the copolyamide of units represented by the structure mole percent and component (B) comprises 5 to 20 mole percent of the copolyamide.

H H O O 4. The linear, fiber-forming copolyamide as defined l l g II in claim 3 wherein R is methyl. NOH HCHz-N 5 5. A textile fiber of the copolyamide of claim 1.

References Cited UNITED STATES PATENTS wherein R is a member of the group consisting of hydro- 8/1955 caflston et gen and alkyl groups containing 1-3 carbon atoms. 10 2,918,454 12/1959 Graham 2. The linear, fiber-forming copolyamide as defined in 3,012,994 12/1961 Bell et claim 1 wherein R is methyl.

3. The linear, fiber-forming copolyamide as defined in WILLIAM SHORT Pnmary Examiner claim 1 wherein component (A) comprises 95 to 8O 15 H, D, ANDERSON, Assistant Examiner. 

